The relationship between polymer side‐chain length and the hole free volume that is effective for solvent diffusion was investigated for polyacrylates and polymethacrylates on the basis of free‐volume theory. Measurements of a polymer's viscoelasticity and solvent diffusivity provided experimental evidence for polymer segment mobility, and the results indicated that hole free volume in a linear polymer increases with hydrocarbon side‐chain length. Because the molecular mechanisms of polymer viscoelasticity and diffusivity are identical, the free‐volume parameters obtained for polyacrylates and polymethacrylates by measuring the polymer viscoelastic‐temperature dependence can reliably be used in predicting the solvent diffusion coefficient.
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Yamaguchi et al. (2003) studied this question.
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